Water-insoluble monoazo-dyestuffs and process for their manufacture



United States Patent OflEice 3,113,938 Patented Dec. 19, 1%63 The present invention provides new water-insoluble monoazo-dyestuflfs and a process for their manufacture; especially it provides the water-insoluble monoazo-dyestuifs corresponding to the following general formula filling wherein X represents a halogen atom, an alltyl, alkoxy, aryloxy or carboxylic acid ester group, Y stands for a halogen atom, a trifluoromethyl, nitro, cyano, carboxylic acid ester, a carboxylic acid amide group which may be substituted, a sulfonic acid ester group, a sulfonic acid amide group which may be substituted, an alkyl sulfonic, aryl sultonic or acyl group, R represents a hydrogen or halogen atom, an alkyl, allroxy or acylamino group, R stands for a hydrogen or halogen atom, an alkyl or alkoxy group and R stands for a hydrogen atom, an alkyl, aralkyl, aryloxyalkyl or vinyl group.

We have found that valuable water-insoluble monoazodyestufis are obtained by coupling the diazonium compounds derived from amines corresponding to the general formula wherein X represents a halogen atom, an alkyl, alltoxy, aryloxy or carboxylic acid ester group and Y stands for a halogen atom, a trifiuoromethyl, nitro, cyano, carboxylic acid ester, a carboxylic acid amide group which may be substituted, a sulfonic acid ester group, a sulfonic acid amide group which may be substituted, an alkylsulfonic, arylsulfonic or acyl group with 2,3-hydroxynaphthoic acid arylides having the general formula wherein R represents a hydrogen or halogen atom, an alkyl, alkoxy or acylamino group, R stands :for a hydrogen or halogen atom, and alkyl or alkoxy group, R stands for a hydrogen atom, an alkyl, arylalkyl, aryloxyalkyl or a vinyl group.

In the process of the present invention there may, generally, be used as coupling components, the arylides of the 2,3-hydroxynaphthoic acid which, in the arylamide radical contain at least one acylamino group with the exception, however, of the benzoylamino group. These compounds may be prepared according to known processes, for example by the condensation of 2,3-hydroxynaphthoic acid with the corresponding amino-acylaminobenzenes in an appropriate solvent, for example in toluene or pyridine, in the presence of a condensation agent, for example, phosphorus trichloride.

The prepartion of the dyestuffs is carried out according to known methods, for example by coupling, in an aqueous medium in the presence of a dispersing agent or in an organic medium, the diazotized aromatic amines with the coupling components.

The new dyestuffs are water-insoluble pigments distinguished by a good fastness to solvents. They are suitable for the preparation of colored lakes or lake formers, for the preparation of solutions or products made of acetyl-cellulose, nitro-cellulose, natural resins or artificial resins, such as polymerisation or condensation resins, for example aminoplasts or phenoplasts, as Well as for the the preparation of solutions or products made of polystyrene, polyolefins, such as polyethylene or polypropylene, polyacryl compounds, polyvinyl compounds, for example polyvinyl chloride or polyethylene terephthalates, rubber, casein and silicon resins.

Furthermore, these new dyestuffs are suitable for pig- Inent printing on a substratum, especially on a textile fiber, as well as on other flat structures such as paper or plastic foils.

The dyestufis obtained according to the process of this invention may also be used for other purposes, for example, finely dispersed in the spinning solution, for dyeing rayon made of viscose or cellulose others or esters, polyamides or polyurethanes or for dyeing paper.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:

Example 1 16.2 parts of l-amino-Z,S-dichlorobenzene are stirred, for some hours WltliSO parts by volume of 5 N hydrochloric acid. Then the solution is diluted with water and ice and, at 0 C., diazotized with 20 parts by volume of a 5 N sodium nitrite solution. The clarified diazo solution is then coupled, at 45 C., with an aqueous suspension of 33.5 parts of 1-(2,3-hydroxynaphthoylamino)-4- acetylaminobenezene obtained by dissolving this com- 17.1 parts of 1-amino-2-chl-orobenzene-S-carboxylic acid-amide are dissolved in the hot in 50 parts by volume of 5 N hydrochloric acid and 175 parts by volume of water and, after the addition of ice, diazotized, at 5 C., with 20 parts by volume of a 5 N sodium nitrite solution. The diazo solution is clarified and, as described in Example 1 coupled with 33.5 parts of l-(2,3-hydroxynaphthoylamino -4-acetylaminob enzene.

When the coupling is complete the precipitated dyestuti is filtered oil, washed and dried. The nitro-cellulose lakes prepared with this. dye-stuff yield a yellowish-red lacquering having a good fastness to overspraying. When incorporating the dyestuit into polyvinyl chloride a yellowish-red dyeing having a good fastness to bleeding is obtained.

Example 3 20.7 parts of 1-amino-2-chlorobenzene-5-sulfonic acidamide are dissolved in the hot in 60 parts by volume of 5 N hydrochloric acid and 150 parts by volume of water 29 parts of 1-am ino-2-methoxybenzene-S-carboxylic acid-(2-methyl-3'-chloro)-phenylaniide are diazotized in the usual manner and, as described in Example 1, coupled with 33.5 parts of 1-(2',3-hydroxynaphthoylamino)-4- acetylaminobenzene. When the coupling is complete the precipitated dyestuli is filtered oti, washed and dried. It

represents a red powder.

The carmine red nitro-cellulose lacquering obtained with this dyestuff has a very good fastness to over-spraymg.

In the following table there are given further dyestufis which can be obtained by using the same coupling component as well as the tints obtained with these dyestuffs:

Diazo component Tint 1-amino-2-chloro-5-nitrobenzene Yellowish- 1-amino-2-methyl-5-nitrobenzene 1 50. l-amino-Z-methoxy-5-nitroben2ene Red. 1-amino-2-chloro,5-trifiuoromethylbenzene Yellowishred.

l-amino-Z-chlorobenzene-5-carboxylic acid-methyl ester Do.

1- a m 1 n o 2 -ch1or0benzene-5-carboxy1ic acid-(2-chloro)- Do.

phenyl ester.

1 a in i n o 2 -chlorobenzene-S-carboxylic acid-(4-chloro)- Red.

phenyl ester. 7

1 a min 2 -chlorobenzene--carboxylic acid-(2-methyl)- Yellowishphenyl ester. red.

1-ammo-2-chlorobenzene-fi-carboxylic acid,phenylamide Do.

1 -amino -2 ohlorobenzene 5 carboxylic aicid (2 methyD- D0.

phenylamide.

l-amino-Z-chlorobeuzene-S-carboxylie acid-(2,4-dimethyl)- D0.

phenylamide.

1-amino-2-ehlorobenzene-5-carbosy1ic acid-(2,5-diclilor0)- D0.

phenylamide.

l-am ino-2-chlorobenzene-ecarboxylic acid-methylamide. Do.

1-ammo-2-methoxybenzene-5'carboxylic acid-methyl estezz. Bluish-red.

1-amin0-2-methoxybenzene-S-carboxylic acid-phenyl ester. Do.

1-armno-2-methoxybenzene-5-carboxylic aeid-(2-chloro)- Do.

phenyl ester.

Diazo component Tint l-amino-Z-methoxybenzene-S-earboxylic acid-amide Carmine 1-amino-2-methoxybenzene-5- carboxylic acid-methylamide Do. l-amino-2-methoxybenzene-5-carboxylic acid-phenylamide. Do. l-amino-2-methoxybenzene-5-carboxylic acid-(2,4- dimeth- D0.

yl)-phenylamide. l-amino-Z-methoxybenzene-5-carboxylic aeid-(2-chl0ro)- D0.

phenylamide. l-amino-2-methoxybenzene-S-carboxylie acld-2-naphthyl- D0. amide. 1-amino-2-methylbenzene 5-carb0xylic acid-methyl ester-"n Red. l-amiuo-Z-methylbenzene-5-carboxylie acid-phenyl ester Do. l-amino-2-methylbenzene-5-earboxylic acid-(2-n1ethyl)- Do.

phenyl ester. 1-amino-2-methylbenzene-5-carboxylic acid-amide Do. l-amino-xmethylbenzene-5-carboxy1ic acid-phenylarnide Do. 1-amino-2-(4-chlor0-phenoxy)-benZene-5-carboxylic acid- Bluish-red.

methyl ester. l amin0-2-(4-chloro-phenoxy)-benzene-5-carboxy1ic acid- Do.

phenyl ester. 1-amino-2-(4-chlorophenoxy)-hcn zene-5-earboxylic acld- Do.

amide. 1-amin0-2-chlorobenzene-S-sulfonic acid-(4-chloro)-phenyl Red.

ester. l-amino-Z-ohlorobenzene-5-sulionic acid-methylamide Do. 1-amino-2-chlor0benzene-5-sulfonic aeid-phenylamide Red. 1-amin0-2-methoxybenrene-S-sulionic acid-phenylamtde. Bluish-red. 1-amino-2-methoxybenzene-S-sulionic acid-diethyl-anude- Do. 1-amino-2-metboxybenzene-fi-sultonic acid-amide. Do. 1-amino-2-methyibenzene-fi-sulionic acid-dimethylamide Red. l-aminoQ-methylbenzene b-sulionic acid-amide Do. 1-amino-2-phenoxybenzene-5-sultonic acid-dimethylamide. Do. l-amino-Q-phenoxybenzene-5-sultonic acid-amide Do. l-aminobenzene-2,5-dicarboxylic acid-dimethylester Do. l-arninofl-chloro-5-cyan0benzene Yelelgwlshr 1-amiuo 2-chloro-5-methylsultonylbenzene D o. 1-amino'2-chlorobenzene-S-carboxylic acid-ethylamide Do. l-amino-Z-ch10ro-5-acetylbenzene l-amino-Z-methylbenzene-S-carboxylic acid-methylamide Example 5 17.1 parts of l-amino-2-cl1lorobenzene-S-carboxylic acid-amide are dissolved in the hot with 50 parts by volume of 5 N hydrochloric acid and parts by volume of water and, after the addition of ice, diazotized, at 5 C., with 20 parts by volume of 5 N sodium nitrite solution. The diazo solution is clarified and, at 50 C., coupled with an aqueous suspension of 34.5 parts of l-(2', 3' hydroxynaphthoylamino)-2-methyl-4-acetylaminobenzcne, obtained by dissolving tln's compound in dilute sodium hydroxide solution and subsequently precipitating with glacial acetic acid in the presence of a reaction product from about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol. When the coupling is complete the precipitated dyestuii is filtered off, washed and'dried. It represents a red powder.

The coupling may also be carried out in the presence of a carrier suited for preparing color lakes.

The nitro-cellulose lakes prepared with this dyestuff yield a red lacquering having a good fastness to overspraying. By incorporating the dyestuff into polyvinyl chloride a red dyeing having a good fastness to bleeding is obtained.

Example 6 17.1 parts of 1-amino-2-chlorobenzen-S-carboxylic acid-amide are diazotized, as described in Example 1. The diazo solution is clarified and coupled, at a temperature between 50 C. and 55 C., with an aqueous suspension of 34.5 parts of 1(2',3'-hydroxynaphthoylamino)-4-propionylaminobenzene obtained by dissolving this solution in dilute sodium hydroxide solution and subsequently precipitating with glacial acetic acid in the presence of a reaction product from about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol. When the coupling is complete the precipitated dyestufi is filtered off, washed and dried. It represents a yellowishred powder.

By incorporating this dyestuff into polyvinyl chloride a yellowish-red'dyeing having a good fastness to bleeding is obtained. The graphic printing prepared with this dyestuif yields an orange-red tint having a good fastness to solvents.

Example 7 19.4 parts of 1-arninobenzene-2-carboxylic acid-methyl ester-S-carboxylie acid-amide are stirred, for some time, With 80 parts by volume of 5 N hydrochloric acid, the paste of chlorine hydrate obtained is diluted with water, cooled with ice to C. and diazotized with parts by volume of 5 N sodium nitrite solution. The clarified diazo solution is entered into a filtered solution of 34.5 parts of 1-(2',3-hydroxynaphthoylamino)-2-methyl-4- acetylaminobenzene in 1000 parts by volume of pyridine. Subsequently the solution is heated to C., the dyestuff formed is filtered off, Washed until the reaction is neutral and dried. A red dyestufi'powder is obtained which dyes polyvinyl chloride yellowish-red tints having a very good fastness to bleeding. The nitro-cellulose lacquering and stoving lacquers prepared with this dyestuff possess a light red tint and a good fastness to oversprayin Example 8 16.6 parts of 1-amino-2-methoxybenzene-5-carboxylic acid-amide are dissolved in 250 parts by volume of water and parts by volume of 5 N hydrochloric acid, cooled with ice to 0- C. and diazotized with 20 parts by volume of 5 N sodium nitrite solution. The clarified diazo solution is entered into a filtered solution of 34.5 parts of 1 (2,3 hydroxynaphthoylamino)-4-propionylaminobenzene in 900 parts by volume of pyridine. When the coupling is complete the solution is diluted With some water, the dyestuif formed is filtered off, washed and dried. A red powder is obtained which dyes polyvinyl chloride carrnine-red tints having a good fastness to selvents.

In the following table are given further components to be used according to the invention as well as the tints of the graphic printings prepared with these dyestufis:

Diazo component Coupling component Tint 1-a.rnino 2-ehlorobenzene-E- 1-(2,3-hydroxynaphthoyl- Yellowishearboxylic acid-amide. ammo)-4-formylaminored.

benzene.

D0 1-(2', 3-hydroxynaphthoyl- Orange,

amin0)-2-chlor0-4aeetylaminobenzene.

Do 1-(2, 3-hydr0:rynaphthoy1- Brown,

amino) 2-methoxy-4- aeetyl-aminobenzene.

Do 1-(2.3-hydroxynaphthoyl- R d,

amine(-3-methoxy-4- acetyhaminobenzenc.

Do 1-(2,3-hydr0xynaphthoyl- R d,

amin0)3-chloro-4- aeetyl-eminobenzene.

Do 1-(2,3"hydroxynaphthoyl- R d,

amino)2-methyl-4-acetylamino-.B-ehlorobenzene.

Do 1-(2,3-hydroxynaphthoyl- R d,

amino)-2,5-dimethyl-4- acetyleminobenzene.

Do 1-(2,3hydrorrynaphth0yl- Red,

amino)-2-methyl-4- propionyl, aminobenzene.

Do 1-(2,3-hydrosynaphthoyl- Red,

amino)2 eh1oro-4-acety1- amino-5-methoxybenzene.

Do 1-(2,3-hydroxynaphthoyl- Yellowishaminofibutyrylamino- Red. benzene.

Do 1-(2,3hydroxynaphthoyl- Red.

amino)-2-methyl-4- butyryl-aminobenzene.

Do 1-(2,3-hydr0xynaphthoy1- Yellowishamin0)-4-phenylacetylred. ammobenzene.

Do 1-(2,3-hydroxynaphthoyl- Red.

amino) 3,4-0:ralylaminobenzene.

l-amino-2-chlorobenzene-5- 1-(2,3-hydroxynaphthoy1- Red.

carboxyiic aeid-methylamino)-2-methyl-4-acetylam e. eminobenzene.

l-amino-Z-chlorobenzene-5- l-(2,3-hydroxynaphthoyl- Red.

earboxylic acid-phenylamin0)-4-propionylaminoamide. benzene.

l-amino-Z-chlorobenzene-5- l-(2,3-hydroxynaphtboyl- Yellowishcarboxylie acid-methyl amino)-2-methyl-4-acetylred. ester. aminobenzene.

Diazo component Coupling component Tint LaminoQ-methoxyben- 1-(2,3-hydroxynaphthoyl- Carmine.

zene-fi'earboxylic acldamino) -2-methyl-4-acetylamide. aminobenzene.

D0 1-(2,3-hydroxynaph h0yl- Do.

. amino)-2-metl1oxy-4- acetylaminobenzene.

D0 1-(2,3-hydroxynaphthoyl- D0.

. amine)-2-metl10xy-4- aeetylamino-S-chlorobenzene.

D0 1-(2',3-hydroxynaphth0yl- Do.

amino) 2-chlor0-4-acety1- amino-s-methoxybenzene.

D0 1-(2,3-hydroxynaphthoyl- Do.

amino)-2-methoxy-4-propionylaminobenzene.

D0 1-(2,3-hydrexynaphthoyl- Do.

amino)-2-methy1-4-acety1- amino-B-methoxybenzene.

D0 1-(2,3-hydroxynaphthoyl- Do.

amino) 4-butyrylaminobenzene.

D0 1-(2,3-hydroxynaphth0yl-- Do.

amino)-4-phenylecetylaminobenzene.

D0 1-(2,3-hydroxynaphthoyl- Do.

amlno)-4-phenoxyacetylaminobenzene.

D0 1-(2,3-hydroxynaphthoyl- Do.

amino)-3,4-oxalylamino-- benzene.

1-amino-2metboxybenzene- 1-(2',3-hydroxynephthoyl- Claret.

fi-earboxylie acid-phenylamino)-3,4-bis-acety1- amide. aminobenzene.

D0 1-(2,3-hydroxynaphthoyl- Carmine. 7 amino)-2,4-bis-acetylaminobenzene. 1-emin0-2-methoxybenzene- 1-(2,3-hydrorynaphthoy1- D frcarboxylic acid-methyl amino)-2-methoxy-4'aceester. tylaminobenzene. 1-amino-Z-methoxybenzenedo Do.

fi-carboxylic acid-methylam e. 1-amino-2-ethoxybenzeue-5- 1-(2,3-hydroxynaphthoyl- Do.

carboxylic acid-amide. amino)-4-acetylamino benzene. 1-amino-2methy1benzene-5- 1-(2,3-hydroxynaphthoyl- Red.

carboxylie acid-amide. amino)-2-meth0xy4-acetyl-aminobenzene.

Do 1-(2,3-hydroxynaphthoyl- Red.

amino)-2-meth0xy'4-acetyl-amino-5-ehlorobenzene.

Do 1-(2,3-hydroxynaphthoyl- Red.

amino)-4-propionylaminobenzene.

Do 1-(2,3-hydroxynaphthoyl- Red.

amino)-4-phenylacetylaminobenzene.

Do 1-(2,3-hydroxynaphthoyl- Bluishamino)-3,4roxalylaminor d, benzene.

1-aminobenzene-2,5-dicar- 1-(2,3-hydroxynaphthoyl- R d,

boxylic aeid-dimethyl aminM-Z-methyl-iacetylester. aminobenzene.

D0 1-(2,3-hydroxynaphthoyl- Red.

amlnobipropionylaminobenzene.

1-amin0-2-(4-chloro)-phe- 1-(2,3-hydroxynaphthoyl' R d,

noxybenzenefi-carboxylic amino)-2-methyl-4-acetylacid-amide. aminobenzene.

1-arnino-2-(4'-chloro)- Red,

phenoxybenzene-scarboxylie acid-methyl ester.

1-amino-2-cbl0robenzenedo R d.

fi-sulfonic acid-amide.

D0 1-(2,3-hydroxynaph- Yellowishthoylamino)-4-propionred. ylaminobenzene.

D0 1-(2,3-hydroxynaph- Do.

thoylamino)-4-butyry1- aminobenzene.

l-amino-Z-chlorobenzene- 1-(2,3'-hydrox3u1aph- Do,

5-su1fonic acidanethylthoylamino)4-propionamide. ylaminobenzene. 1-amin02-methoxyben- 1-(2,3-hydr0xynaph- Carmine,

zene-S-sull'onic acid-amide. thoylamino)-2-methoxy4- acetylaminobenzene.

D0 l-(2,3-hydroxynaph- D thoylamino)-2-methoxy-4- acetylamino-dchlorobenzene.

D0 1'(2,3-hydr0xy11aph- D thoylamino)-2-methyl- 4-acety1amino-5-methoxybenzene.

Do 1-(2,3-l1ydr0xynaph- D0,

thoylamino)-4 -propionylaminobenzene.

Do 1-(2,3-hydroxynaph- Do.

thoy1arnin0)-3,4-oxalylaminobenzene.

1-amino-2-methoxyben- 1-(2,3-hydroxynaph- Do.

zene-5-su1ionic acid-meth thoylamino)-2-methorwylamide. i-acetylaminobenzene. 1-amino-2methoxyben- 1-(2,3-hydro)wnaph- D0.

zene fi-sulto nic acid-diethylamide.

thoylamino)-2-methoxy- 4-acety1amino-5-chlorobenzene.

Dlazo component Coupling Component Tint l-aminoZ-methylben- 1-(2,3-hydroxynaph- Red.

zene-E-sulfomc acid-amide. thoylamino)-2-methyl- 4-acetylaminobenzene.

Do 1-(2,3-hydroxynaph- Red.

thoylamino) -2-methoXy-4- acetylaminobenzene.

Do 1-(2 3-hydroxynaph- Red.

tohylamino)-4-pr0pionylaminobenzene.

Do 1-(2,3-hydroxynaph- Red.

thoylamino)-3,4-oxalylaminobenzene.

We Glam:

1. The water-insoluble monoazo-dyestuffs having the following formula wherein X is a member selected from the group consisting of chlorine, lower alkoxy, phenoxy, chlorophenoxy and a carboxylic acid alkyl ester group, A is a member selected from the group consisting of a corbonyl and sulfonyl group, R is a member selected from the group consisting of hydrogen, lower alkyl, phenyl, methylphenyl, chlorophenyl, dimethylphenyl and dichlorophenyl, R is a member selected from the group consisting of hydrogen, chlorine, lower alkyl, lower alkoxy and acetylamino, R is a member selected from the group consisting of hydrogen, chlorine, lower alkyl and lower alkoxy, and R is a member selected from the group consisting of hydrogen, lower alkyl, benzyl and phenoxymethyl.

2. The water-insoluble monoazo-dyestuff having the formula '3. The water-insoluble monoazo-dyestuff having the formula 4. The water-insoluble monoazo-dystuifs having the formula 5 I C O-NHz cH ooc l :fi I III 5. The Water-insoluble monoazo-dyestufl? having the formula w N I 6. The water insoluble monoazo-dyestuif having the formula 0-0 ONHa (EH30- I II N l c O-NHNHG O-OHz References Cited in the file of this patent UNITED STATES PATENTS 2,025,582 Fischer Dec. 24, 1935 2,060,163 Bonhote Nov. 10, 1936 2,252,844 Fischer et al. Aug. 19, 1941 2,262,464 Marriott et al Nov. 11, 1941 2,742,459 Fischer Apr. 17, 1956 2,899,421 Fischer Aug. 11, 1959 FOREIGN PATENTS 7 818,675 France Oct. 1, 1937 

1. THE WATER-INSOLUBLE MONOAZO-DYESTUFFS HAVING THE FOLLOWING FORMULA 